Including finishing agents in at least one of two mutually immiscible solutions containing coreactants and serially applying said solutions to fibrous materials



United States Patent INCLUDING FINISHING AGENTS IN AT LEAST ONE OF TWOMUTUALLY IMMISCIBLE SO- LUTIONS CONTAINING COREACTANTS AND SERIALLYAPPLYING SAID SOLUTIONS TO FIBROUS MATERIALS William L. Wasley,Berkeley, and Robert E. Whitfield and Lowell A. Miller, Walnut Creek,Calif., assignors to the United States of America as represented by theSecretary of Agriculture No Drawing. Filed May 29, 1962, Ser. No.198,653

The portion of the term of the patent subsequent to Feb. 19, 1980, hasbeen disclaimed US. Cl. 8-115.6 19 Claims Int. Cl. D06m 13/54 Anon-exclusive, irrevocable, royalty-free license in the invention hereindescribed, throughout the world for all purposes of the United StatesGovernment, with the power to grant sublicenses for such purposes, ishereby granted to the Government of the United States of America.

This invention relates in general to finishing of textiles. The objectsof the invention include novel processes of applying finishing agents totextiles and other fibrous materials. Further objects of the inventionwill be obvious from the following description wherein parts andpercentages are by weight unless otherwise specified.

In the processing of textiles it is conventional practice to applyfinishing agents to impart a desired property or characteristic to thetextile. For example, the textile may be impregnated with an insecticidesuch as dieldrin so that the fabric will be resistant to attack byinsects. Other finishing agents may be applied to enhance thewaterrepellancy or oil-repellancy of the fabric, to increase itsresistance to becoming soiled, to make it resistant to attack by fungi,to render it softer, to give it a desired color or luster, to provide itwith a specified odor, etc. Ordinarily, these finishing agents areapplied by a system which involves dispersing the agent in a volatileliquid carrier, immersing the fabric in the resulting dispersion andthen drying the fabric to evaporate the volatile carrier and leave thefinishing agent on the fabric. Such techniques have the disadvantagethat the treatment is only temporary. When the fabric is subjected tolaundering or dry-cleaning, the finishing agent is removed so that ifthe same quality is desired in the cleaned fabric, the finishing agentmust be re-applied. This is a very common practice; for example, withraincoats where the waterrepellant finishing agent must be renewed eachtime that the garment is dry-cleaned.

In the copending application of Miller, Whitfield, and Wasley, Ser. No.98,718, filed Mar. 27, 1961, now Patent No. 3,078,138, granted Feb. 19,1963, there are disclosed processes for shrinkproofing wool wherein acondensation polymertypically a polyamideis formed in situ on the woolfibers and grafted to the wool, that is, chemically combined therewith.In a typical embodiment of the process, a wool fabric is seriallyimpregnated with two solutions-one being a solution of a diamine inwater, the other being a solution of a diacid cholride in awaterimmiscible, volatile, inert solvent. By such treatment the fibersare coated with superposed layers of the mutuallyinsoluble solutions,for example, an inner layer of diamine in water and an outer layer ofdiacid chloride in water-immiscible solvent. Under these conditions thediamine and diacid chloride react almost instantaneously at theinterface between the phases, producing in situ on the fibers ahigh-molecular weight, resinous polyamide which coats the fibers andrenders the fabric shrinkproof without detriment to the hand, porosity,and other valuable properties of the fabric. Moreover, the polyamide ischemically bonded to the wool so that the shrinkproof- 3,429,650Patented Feb. 25, 1969 ing effect is highly durable, i.e., the polyamidedeposit is not removed by repeated washing of the treated fabric inconventional soap and water or detergent and waterlaunderingformulations, or in conventional dry-cleaning formulations. From aprocedural standpoint, the process has the advantage of simplicity andrapidity in that the basic operation is simply a serial impregnation ofthe fabric in the two solutions. Another point is that the process doesnot require any heat curing of the treated fabric as is commonlynecessary in most resin shrinkproofing procedures.

It has now been found that the interfacial polymerization systemdescribed above can be adapted for applying finishing agents of manykinds to textiles. In accordance with the present invention, finishingagents are applied to textiles by a procedure which locks the agent tothe textile fiber so that the quality imparted to the textile by theselected agent is durable in that the textile can be repeatedlylaundered or dry-cleaned without removal of the finishing agent.Accordingly, a primary object of the present invention is the provisionof processes whereby textiles may be provided with durable finishes.This object is attained by a process which involves forming, underinterfacial polymerization conditions, an organic condensation polymerin situ on the fibers of the textiles while providing a textilefinishing agent at the locus where the interfacial polymerization takesplace. As a result of such procedure, the finishing agent is entrappedor enmeshed in the polymer as it is formed and is thus securely lockedto the fibers of the textile. In a typical embodiment of the invention,a wool textile is first impregnated with an aqueous solution ofhexamethylene diamine. Then the textile is impregnated with a solutioncontaining sebacoyl chloride and dieldrin in a water-immiscible solvent,such as toluene. By such treatment the fibers are coated with superposedlayers of the mutuallyinsoluble solutions. Under these conditions thediamine and the diacid chloride (sebacoyl chloride) react almostinstantaneously at the interface between the two phases, producing insitu on the fibers a high molecular weight, resinous polyamide which ischemically bonded to the fibers and which enmeshes the dieldrin. The netresult is that the treated fabric is not only shrinkproof but it isresistant to attack by moths. Moreover, these qualities are durable inthat the treated fabric can be subjected to dry-cleaning or washing inaqueous media and still retain its characteristics of being shrinkproofand resistant to insect attack.

The invention is of wide applicability and can be employed for fixingfinishing agents of all kinds to textiles. Typical examples of suchagents are: antiseptics, antistatic agents, agents for imparting fireorflame-resistance, insecticides, insect repellents, lubricants, textileconditioners or softeners, odorants, deodorants, pigments or othercoloring agents, sizing agents, oil repellents, water repellents, soilrepellents, and the like. Agents to perform such functions are wellknown in the art and form no part of the present invention.Nevertheless, examples of particular materials which may be applied toachieve desired qualities in the treated fabric are provided belowmerely by way of illustration and not limitation.

Agents for imparting resistance to flame or fire.-Sodium borophosphate,ammonium sulphamate, chlorinated diphenyl, chlorinated paraffin, thebromoform adduct of triallyl phosphate, etc.

Antiseptics, that is, agents which impart to the textile resistanceagainst attack by mildew, fungi, bacteria, or other forms ofmicroorganisms.Beta naphthol, o-phenylphenol, 2,4,5-trichlorophenol,2-bromo-4-phenylphenol, tetrachlorophenol, pentachlorophenol,4-chloro-2-phenylphenol, 6-chloro-2-phenylphenol, sodiumo-phenylphenate, sodium 2,4,5-trichlorophenate, sodiumtetrachlorophenate,

sodium pentachlorophenate, lauryl pyridinium chloride, 2,2dihydroxy-S,5'-dichloro-diphenylmethane, salicylanilide, quaternaryammonium compounds such as dodecyl dimethyl benzyl ammonium chloride,sodium dimethyl dithiocarbamate, lauryl amine salt of tetrachlorophenol,dodecylamine salt of lactic acid, dodecyl amine salt of salicylic acid,etc.

Soil repellents.-These agents may be of the types effective againstwater-borne soil or oil-borne soil or they may be effective against bothkinds of soil. Typical materials which may be used are: emulsions ofwaxes and aluminum acetate or zirconium acetate; silicone compounds suchas polydimethyl siloxanes, polymethylhydrogen siloxanes, fluorinatedcompounds such as polyvinyl perfluorobutyrate, polyperfluorobutylacrylate, chromium complexes of perfluorinated aliphatic carboxylicacids such as those of the formula:

CF (CF COOH Oil repellents-Chromium complexes of perfluorinatedaliphatic carboxylic acids such as those of the formula:

CF (CF COOH fluorinated compounds such as polyvinyl penfluorobutyrate,polyperfluorobutyl acrylate, copolymers of vinyl perfluorobutyrate andperfluorobutyl acrylate.

Water repellents-Waxes; aluminum acetate; zirconium acetate; emulsionsof waxes and aluminum or zirconium acetate; chlorinated paraflin waxes,for instance, those containing 42 to 70% chlorine; aluminum soaps; cetylpalmitate; stearyl stearate; silicone compounds such aspolydimethylsiloxane and polymethyl hydrogen siloxane.

Insecticides.p-Dichlorobenzene; silicofluorides such as sodiumsilicofiuoride; pyrethrins; dieldrin;pentachlorodihydroxy-triphenylmethane sodium sulphonate; extract ofderris root; pentachlorophenol; dinitronaphthol, dinitroorthocresol,benzene hexachloride; D.D.T.; N,N-diethyl- N-acetyl thiocarbamosulfenamide, N,N-diphenyl-N'- acetyl thiocarbamo sulfenamide.

Insect repellents.--N-ethyltoluamide; 2-ethyl-1,3-hexanediol; dimethylphthalate; dimethyl carbate (Dimelone); butopyronoxyl; etc.

Sizing agents.Starches, gums as tragacanth, karaya, arabic, etc., methylcellulose, sodium carboxymethylcellulose, sodium alginate, gelatin,polyvinyl alcohol, polyvinyl acetate, polyacrylic acid, sodiumpolyacrylate, etc.

Pigments or other coloring materials.Typical among these areconventional dyes such as those of the acid, direct, sulphur, andsolvent types. However, the invention is of particular advantage in thatpigments-that is, coloring materials which are not classed as dyescan bedurably fixed to textile materials. Typical of such pigments are bariumchromate, strontium chromate, zinc chromate, venetian red, turkey red,indian red, carbon black, siennas, umbers, ochres, cinnabar (red mercurysulphide), powdered metals such as aluminum, copper, brass, bronze,zinc, gold, titanium dioxide, zinc oxide, lithopone, basic leadcarbonate, basic lead sulphate, pigment yellow 1 (CI11680), pigmentyellow 34 (CI- 77600), pigment orange 5 (CI-12075), pigment orange 13(CI-21110), pigment red 4 (CI-12085), pigment red 101 (CI-77015),pigment blue 15 (CI-74160), pigment green (CI-74260), pigment brown(CI-12480), and pigment red 106 (CI-77766). The invention is alsoadapted for fixing to textiles fluorescent brightening agents (theso-called optical bleaches), for example, those listed in the ColourIndex under Nos. 40,630, 40,600, 40,620, 40,605, and 40,640. A specialadvantage of the invention involves fixing a white pigment, such astitanium dioxide, to wool textiles whereby the product is less readilyyellowed by exposure to light than is the untreated fabric. Also, suchproduct is measurably whiter than the untreated fabric as shown byreflectance tests, particularly when the reflectance is measured over adark background.

Softeners, often referred to as lubricants or conditioners.Fatty acidesters of diethylene glycol such as the lauric or stearic acid esters,polyethylene glycols, sulphonated animal or vegetable fats, highmolecular weight aliphatic alcohols such as decyl alcohol, oleylalcohol, dodecyl alcohol, cetyl alcohol, blends of waxes and sulphonatedoils, fatty acids such as stearic and palmitic, derivatives of sorbitolsuch as sorbitan monolaurate, monopalmitate, monostearate, condensationproducts of fatty acids and alkylolamines, fatty acid esters of ethyleneglycol monoalkyl ethers such as the oleic acid, stearic acid, orpalmitic acid esters of monobutyl ether of ethylene glycol, condensationproducts, of fatty acids and amino sulphonic acids; for example, thesodium salt of N-oleoyl taurine, quaternary compounds such asstearamidomethyl pyridinium chloride, and octadecyloxymethyl pyridiniumchloride.

Antistatic agents, that is, agents which will reduce the tendency oftextiles to develop static electrical charges.- Polymers ofbeta-propiolactone; gamma-stearamidopropyl dimethyl heneicosaethenoxyammonium chloride; gammastearamidopropyl dimethyl nonaethenoxy ammoniumchloride; gamma-stearamidopropyl di(dodecaetheneoxy) ammonium chloride;gamma-stearamidopropyl tri-dodecaetheneoxy) ammonium chloride; N-cetylN-ethyl morpholinium ethosulphate; etc.

In applying the process of the invention, the textile to be treated issuccessively impregnated with two solutions, each containing one of thepair of complementary condensation polymer-forming intermediates. Thefinishing agent to be applied to the textile may be added to either ofthe solutions, or, it may be added to both. Depending on the particularcase, it may be preferred to add the finishing agent to one or the otherof the solutions. For example, if the finishing agent is water-solubleis would be preferable to add it to the solution which contains water asa solvent. On the other hand, if the finishing agent is Water-insolublebut soluble in organic solvents it would be preferable to add it to thatsolution which contains an organic solvent. However, it is not essentialthat the finishing agent be actually dissolved; it is only necessarythat it be present. Thus the agent may be dissolved, suspended, or inany other dispersed form. It is also evident that it is within thepurview of the invention to add more than one finishing agent; forexample, one may add both a soil-repellent and an insecticide, or both asoil-repellent and a coloring material. Further extensions of thisconcept will be obvious from these examples. The amount of finishingagent to be used will vary depending on such factors as the efficacy ofthe agent selected, the characteristics to be imparted to the textile,and so forth. In general, theamount of finishing material may beproportioned so that the product contains anywhere from 0.01 to 10% offinishing agent, based on the weight of the textile, per se. The textilematerial to which the process of the invention is applied may be in theform of bulk fibers, slivers, rovings, yarns, felts, woven textiles,knitted textiles, or even completed garments or garment parts.

By a suitable choice of the complementary polymerforming reagents onecan utilize many different types of polymers for fixing the selectedfinishing agent to the textile substrate. Reagents suitable for thispurpose and methods of applying them are described in our copendingapplication, Ser. No. 98,718, filed Mar. 27, 1961, of which thisapplication is a continuation-in-part. However, this material isreiterated herein for the sake of completeness of disclosure. Theparticular polymer-forming reagents-- herein termed Component A andComponent Bwhich are to be used will depend on the type of polymerdesired. In general, Component A may be a diamine, a diol, or a mixtureof a diamine, and a cliol. Dependent on the reagent selected asComponent A, Component B may be, for example, a diacid chloride, abischloroformate, a diisocyanate, or mixtures of these classes ofcompounds. Typical choices which may be made and the type of polymerformed are set forth below by way of example:

ents of Component A are soluble in water and may thus be applied to thetextile in aqueous solution. In such case Since components A and B maybe selected to form any desired type of condensation polymer, thesecomponents may be aptly termed as complementary organic condensationpolymer-forming intermediates. They may further be appropriatelydesignated as fast-reacting or direct-acting because they form theresinous polymers rapidly and directly under interfacial conditionswithout requiring any aftertreatments, such as treatment with curingagents, oven cures, etc.

Having selected the desired Components A and B, these are formed intoseparate solutions for application to the textile to be treated. Anessential consideration in the preferred modification of the inventionis that the solvents used in the respective solutions of Components Aand B be substantially mutually immiscible so that a liquidliquidinterface will be set up between the two solutions on the wool fibers.Thus, for example, Component A is dissolved in water and Component B isdissolved in benzene, carbon tetrachloride, toluene, xylene, ethylenedichloride, chloroform, hexane, octane, petroleum ether or othervolatile petroleum distillate, or any other inert waterimmisciblesolvent. (As set forth hereinabove, the selected finishing agents to befixed to the textile are dispersed in either or both of thesesolutions.) The two solutions are then applied to the textile serially;that is, the textile is treated first with one solution, then with theother. The order of applying the solutions is not critical. Generally,the solution of Component A is applied first and the solution ofComponent B is applied next; however, the reverse order gives goodresults and it is within the ambit of the invention to apply thesolutions in either sequence.

The solutions may be applied to the textile in any desired way as longas they are applied serially. A preferred method involves immersing thetextile in one solution, removing excess liquid as by use of squeezerolls, immersing the textile with the second solution, again removingexcess liquid, rinsing the treated fabric in water and then drying it.Conventional apparatus consisting of tanks, padding rolls, squeezerolls, and the like, are generally used in applying the respectivesolutions. The amount of each solution applied to the textile may bevaried by altering the residence time in the solutions, the pressureexerted by the squeeze rolls and by varying the concentration of theactive materials in the respective solutions. To decrease carry-over ofthe solvent from the first treating solution to the second solution, thetextile after its immersion in the first solution may be subjected todrying conditions such as a current of warm air to concentrate thesolution carried by the fibers.

As noted above, a critical factor in the preferred form of the inventionis that the complementary agentsComponent A and Component B (plus theadded finishing agents)are serially applied to the textile dispersed insolvent, which are substantially mutually immiscible, whereby to secureinterfacial polymerization conditions. The nature of the solvents is ofno consequence as long as they are essentially inert and possess theabove-stated property of substantial immiscibility. Usually, volatilesolvents are preferred as they may be removed from the treated textileby evaporation. However, non-volatile solvents can be used, in whichcase they may be removed from the product by extraction with suitablevolatile solvents therefor or Washed outwith soap and water or detergentand water formulations. In many cases the ingredithe solvent forComponent B may be any inert, essentially water-immiscible organicsolvent. Typical illustrative examples thereof are benzene, toluene,xylene, carbon tetrachloride, ethylene dichloride, chloroform, hexane,octane, petroleum ether or other volatile petroleum fraction. It is,however, not essential that Component A be employed in aqueous solution.Thus, one may utilize a system of two essentially immiscible organicsolvents, Component A being dispersed in one solvent and Component B inthe other. As an example, Component A may be dispersed in 2-bromoethylacetate and Component B dispersed in benzene. Another example involvesusing formamide, dimethylformamide, or dimethylformamide as the solventfor Component A and using n-hexyl ether as the sol vent for Component B.A further example involves a system of adiponitrile as the solvent forComponent A and ethyl ether as the solvent for Component B. Examples ofother pairs of solvents which are substantially immiscible with oneanother and which may be used for preparing the solutions of therespective reactants are 2-bromoethyl acetate and n-hexyl ether,ethylene glycol diacetate and n-hexyl ether, adiponitrile and n-butylether, adiponitrile and carbon tetrachloride, benzonitrile andformamide, n-butyl ether and formamide, di-N-propyl aniline andformamide, isoamyl sulphide and formamide, benzene and formamide, butylacetate and formamide, benzene and nitromethane, n-butyl ether andnitromethane, carbon tetrachloride and formamide, dimethyl aniline andformamide, ethyl benzoate and formamide.

The concentration of polymer-forming reagents (Component A and ComponentB) in the respective solutions is not critical and may be varied widely.Generally, it is preferred that each of the pair of solutions containsabout from 1 to 20% of the respective active component. In applying theprocess of the invention, enough of the respective solutions are appliedto the textile to give a polymer deposit on the fibers of about 1 to 10% Such amounts of polymer applied on wool afford a substantial degreeof shrinkproofing with no significant reduction in the hand of the wool.Greater amounts of polymer may be deposited on the textile, particularlyin those cases where it is not desired to maintain the natural hand ofthe textile. The relative amounts of Component A and Component B appliedto the textile may be varied as desired for individual circumstances.Generally, it is preferred to apply the components in equimolarproportions; that is, the amounts are so selected that there are thesame number of functional groups provided by Component A as pro vided bythe functional groups of Component B.

It is often desirable to add reaction promoters or catalysts to eitherof the solutions of Component A or B in order to enhance reactionbetween the active agents. For example, in cases where the systeminvolves reaction between a diamine (or a diol) and a diacid chloride ora bischloroformate it is desirable to add to either of the solutions asufiicient amount of alkaline material to take up the HCl formed in thereaction. For such purpose one may use a tertiary amine such aspyridine, dimethyl aniline, or quinoline or an alkali-metal hydroxide,or, more preferably, an alkaline material with buffering capacity suchas sodium carbonate, sodium bicarbonate, trisodium phosphate, borax,etc. Another plan which may be used in instances where Component Aincludes a diamine and Component B includes a diacid chloride orhischloroformate, involves supplying the diamine in excess so that itwill act both as a reagent and as an HCl-acceptor. The reaction ofComponents A and B may also be catalyzed by addition of such agents astributyl tin chloride, stannous tartrate, ferric chloride, titaniumtetrachloride, boron trifluoride-diethyl ether complex, or tin salts offat acids such as tin laurate, myristate, etc. Such catalysts areparticularly useful to promote reaction between (1) diols and (2)diisocyanates, diacid chlorides, and bischloroformates.

Where one of the solutions of the reactants contains water as thesolvent, it is often desirable to incorporate a minor proportion of asurface-active agent to aid in dispersing the reactant and to assist inpenetration of the solution into the textile. For this purpose one mayuse such agents as sodium alkyl (Cg-C18) sulphates, the sodium alkane (C-C sulphonates, the sodium alkyl (C C benzene sulphonates, esters ofsulphosuccinic acid such as sodium dioctylsulphosuccinate, and soaps,typically sodium salts of fat acids. Emulsifying agents of the non-ionictype are suitable, for example, the reaction products of ethylene oxidewith fatty acids, with polyhydric alcohols, with partial esters of fattyacids and polyhydric alcohols or with alkyl phenols, etc. Typical ofsuch agents are a polyoxyethylene stearate containing about 20oxyethylene groups per mole, a polyoxyethylene ether of sorbitanmonolaurate containing about 16 oxyethylene groups per mole, adistearate of polyoxyethylene ether of sorbitol containing about 40oxyethylene groups per mole, iso-octyl phenyl ether of polyethyleneglycol, etc. Generally, only a small proportion of surface-active agentis used, on the order of 0.05 to 0.5%, based on the weight of thesolution. In addition to, or in place of the surface-active agent, asupplementary solvent may be added to the primary solvent (water) inquantity suflicient to disperse the active reactant. For such purposeone may employ acetone, or other inert volatile solvent, particularlyone that is at least partially miscible with water. It is evident thatthe solutions of Components A and B need not necessarily be truesolutions; they may be colloidal solutions, emulsions, or suspensions,all these being considered as solutions for the purposes of the presentinvention.

Ordinarily, the treatment of the textile with the solutions of thecomplementary agents is carried out at room temperature as at suchtemperature the polymerization takes place very rapidly, that is, in amatter of a minute or less. If, however, a higher rate of polymerizationis desired-as in continuous operation on long lengths of cloththe secondsolution may be kept hot, for example, at a temperature up to around 150C. Also, where the agents used include a diol as such (in contrast tothe alkali salt thereof) it is preferable to heat the second solution asthe polymerization rates with the diols are generally unsatisfactory atroom temperature.

It will be obvious to those skilled in the art that for best results,the finishing agent and the polymer-forming intermediate which areemployed together in the textiletreating solutions be selected forcompatibility. For example, in the solution which contains Component A(a diamine or a diol) one would avoid using a finishing agent which isreactive with amine or hydroxy groups. Thus typically, the selectedfinishing agent should be free from such functional groups as acid, acidchloride, or isocyanate radicals. Moreover, with the solution containingthe complementary polymer-forming intermediate (Component Bdiacidchloride, bischloroformate, or diisocyanate) one would not use afinishing agent which contained a reactive functional group such asamino or hydroxyl. Taking into account these considerations, if it isdesired to apply a finishing agent containing a radical reactive withamines or hydroxy compounds, one would add it to the solution containingthe diacid chloride, bischloroformate, or diisocyanate. Conversely, ifone desired to apply a finishing agent containing a radical reactivewith acid chlorides or isocyanates, one would add it to the solution ofthe diamine or diol.

COMPONENTS A AND B As noted briefly above, the selection of Components Aand B depends on the type of polymer desired to be formed on the fibers.In general, Component A may be a diamine, a diol, or a mixture of adiamine and a diol; Component B may the a diacid chloride, abischloroformate, a diisocyanate, or a mixture of two or more of theseclasses of compounds. Typical examples of compounds which can beemployed as Component A in a practice of the invention are describedbelow.

As the diamine one may employ any of the aromatic, aliphatic, orheterocyclic compounds containing two primary or secondary amine groups,preferably separated by at least two carbon atoms. The diamines may besubstituted if desired with various non-interfering (non-functional)substitnents such as ether radicals, thioether radicals, tertiary aminogroups, sulphone groups, fluorine atoms, etc. Typical compounds in thiscategory are listed below merely by Way of illustration and not by wayof limitation: ethylene diamine, trimethylene diamine, tetramethylenediamine, hexamethylene diamine, octamethylene diamine, decamethylenediamine, N,N'-dimethyl l, 3 propanediamine, 1,2 diamino 2 methylpropane,2,7 diamino 2,6-dimethyloctane, N,N' dimethyl 1,6 hexanediamine,1,4-diamino cyclohexane, 1,4-bis (aminomethyl) cyclohexane,2,2'-diaminodiethyl ether, 2,2'-diaminodiethyl sulphide, ibis(4-aminocyclohexyl) methane, N,N-dimethyl- 2,2,3,3,4,4hexafluoropentane-l,S-diamine, ortho-, meta-, or para-phenylene diamine,benzidine, xylylene diamine, m-toluylene diamine, ortho-tolidine,piperazine, and the like. If desired, mixtures of different diamines maybe used. It is generally preferred to use aliphatic alpha, omegadiamines, particualrly of the type wherein n has a value of 2 to 12,preferably 6 to 10.

As the diol one may employ any of the aliphatic, aromatic, orheterocyclic compounds containing two hydroxy groups, preferablyseparated by at least two carbon atoms. The diols may be substituted ifdesired with various noninterfering (non-functional) substituents suchas ether groups, sulphone groups, tertiary amine groups, thioethergroups, fluorine atoms, etc. Typical compounds which may be used arelisted below merely by way of illustration and not limitation: Ethyleneglycol, diethylene glycol, 2,2- dimethyl propane-1,3-diol,propane-1,3-diol, butane-1,4- diol, hexane-1,6-diol, octane-1,8-diol,decane-LlO-diol, dodecane-hlZ-diol, butane-1,2-diol, hexane-1,2-diol,1-0- methyl glycerol, Z-O-methyl glycerol, cyclohexane-1,4-diol,hydroquinone, resorcinol, catechol, =bis(parahydroxyphenyl) methane,1,2-Ibis(parahydroxyphenyl) ethane, 2,2- bis(parahydroxyphenyl) propane,2,2-bis(parahydroxyphenyl) butane, 4,4dihydroxybenzophenone, naphthalene1,5 diol, biphenyl-4,4'-diol, 2,2-bis(3-methyl-4-hydroxyphenyl) propane,2,2-bis(3 isopropyl 4 hydroxyphenyl) propane,2,2-bis(4-hydroxy-dibromophenyl) pro pane, etc.

If desired, mixtures of different diols may be used. It is also withinthe purview of the invention, though less preferred, to use thecompounds containing more than two hydroxy groups as for example,glycerol, diglycerol, hexanetriol, pentaerythritol, etc. Moreover, it iswithin the spirit of the invention to utilize the sulphur analogues ofthe diols. Thus, for example, instead of using the compounds containingtwo hydroxy groups one can use the analogues containing either (a) twoSH groups or (b) one SH group and one OH group.

Among the preferred compounds are the aliphatic diols, for example,those of the type:

wherein n has a value from 2 to 12. Another preferred category ofaliphatic compounds are the polyethylene glycols, i.e.:

wherein n has a value from zero to 10. A preferred category of aromaticdiols are the bisphenols, that is, compounds of the type R R R cr H 1 1OH wherein RCR represents an aliphatic hydrocarbon group containing 1 to12 carbon atoms and R represents hydrogen or a lower alkyl radical. Inthis category especially preferred compounds are 2,2-lb-is(parahyd'roxyphenyl) propane, often designated as bisphenol-A-2,2-his (3-methyl-4-hydroxyphenyl) propane; 2,2-bis(3-isopropyl-4-hydroxyphenyl) propane; and brominated derivatives of bisphenol A,such as 2,2-bis(4-hydroxy-dibromophenyl) propane.

The diols are employed as such or in the form. of their alkalimetalsalts, that is, as alcoholates or phenolates, depending on whether thediols are aliphatic or aromatic. The alkali-metal derivatives arepreferred as they will react with the active agents of Component B atroom temperature. With the diols, as such, temperatures above roomtemperature are generally required to promote reaction with theircomplements in Component B. In such case proper temperature for thereaction can be achieved by holding the second solution into which thetextile is immersed, at about ,50 to 150 C. It is obvious that thesolvent selected for the second solution will need to be one which has aboiling point above the temperature selected, or, in the alternative, apressurized system can be used to maintain the solvent in the liquidphase.

In the modification of the invention wherein water is used as thesolvent for Component A (a diol in this case) and Component B isdispersed in a water-immiscible, inert solvent, it is preferred to usearomatic diols in their salt (phenolate) form. This affords severaldistinct advantages. Thus the alkali-metal phenolates are quite solublein water, they are relatively stable in aqueous solution (in contrast tothe alcoholates), and they will react at room temperature with diacidchlorides, bischloroformates, or diisocyanates so that no heating isrequired.

Typical examples of compounds which can be employed as Component B in apractice of the invention are described below.

As the diacid chloride one may employ any of the aliphatic, aromatic, orheterocyclic compounds containing two carbonylchloride (COCl) groups,preferably separated by at least two carbon atoms. The diacid chloridesmay be substituted if desired with non-interfering (non-functional)substitutents such as ether groups, thioether groups, sulphone groups,etc. Typical examples of compounds in this category are listed belowmerely by way of illustration and not limitation: Oxalyl chloride,maleyl chloride, fumaryl chloride, malonyl chloride, succinyl chloride,glutaryl chloride, adipyl chloride, pimelyl chloride, suberyl chloride,azelayl chloride, sebacyl chloride, cyclohexane-1,4 biscarbonylchloride,phthalyl chloride, isophthalyl chloride, terephthalyl chloride,4,4'-biphenyl-dicarbonyl chloride, fl-hydromuconyl chloride, i.e.,ClCOCH CH:CHCH -COCl, diglycollic acid chloride, i.e., O(CH COCl) higherhomologues of this compound as ()(CH CH COCl) dithiodiglycollic acidchloride, diphenylolpropanediacetic acid chloride, i.e., (CH C(C H OCHC0Cl) and the like. If desired, mixtures of different diacid chloridesmay be used. It is also evident that the sulphur analogues of thesecompounds may be used and are included within the spirit of theinvention. Thus, instead of using compounds containing two 'COC1 groupsone may use compounds containing one CSC1 and one COC1 group orcompounds containing two -CSCl groups. Moreover, although the diacidchlorides are preferred as they are reactive and relatively inexpensive,the corresponding bromides and iodides may be used.

As the diacid chloride, it is generally preferred to use the aliphaticcompounds containing two carbonylchloride groups in alpha, omegapositions, particularly those of the type:

ClCO(CH COCl wherein n has a value from 2 to 12. Another preferredcategory includes the compounds of the formula ClCOAOOCl (where A is thebenzene or cyclohexane radical), especially para-substituted compoundssuch as terephthalyl and hexahydroterephthalyl chlorides.

As the bischloroformate one may use any of the aliphatic, aromatic, orheterocyclic compounds containing two chloroformate groups preferablyseparated by at least two carbon atoms. The bischloroformates may besubstituted if desired with noninterfering (nonfunctional) substitutentssuch as sulphone groups, ether groups, thioether groups, etc. Typicalexamples of compounds in this category are listed below merely by way ofillustration and not limitation: Ethylene glycol bischloroformate,diethylene glycol bischloroformate, 2,2-dimethyl propane 1,3-diolbischloroformate, propane-1,3-diol bischloroformate, butane-1,4-diolbischloroformate, hexane-1,6-diol bischloroformate, octane- 1,8-diolbischloroformate, decane-1,10-diol bischloroformate, butane-1,2-diolbischloroformate, hexane-1,2- diol bischloroformate,lmethoxyglycerol-1,3-bisch1oroformate, glycerol-1,2-bischloroformate,glycerol-1,3-bischloroformate, digylcerol bischloroformate, hexanetriolbischloroformate, pentaerythritol bischloroformate, cyclohexane-l,4-diolbischloroformate, hydroquinone bischloroformate, resorcinolbischloroformate, catechol bischloroformate, bischloroformate of2,2-bis(parahydroxyphenyl) propane, bischloroformate of2,2-bis(parahydroxyphenyl) butane, bischloroformate of4,4-dihydroxybenzophenone, bischloroformate of1,2-bis(parahydroxyphenyl) ethane, naphthalene-1,5-diolbischloroformate, biphenyl-4,4'-diol bischloroformate, etc. 1f desired,mixtures of different bischloroformates may be used.

Among the preferred compounds are the aliphatic bischloroformates, forexample, those of the type:

of aromatic bischloroformates are the bisphenol chloroformates, that is,compounds of the type:

u 1 u R wherein RCR represents an aliphatic hydrocarbon group containing1 to 12 carbon atoms and R is hydrogen or a low alkyl radical.

It is also evident that the sulphur analogues of the bischloroformatesmay be used and such are included within the spirit of the invention.Thus, instead of using the compounds containing two groups one may useany of the compounds containing the sulphur analogues of these groups,for example, the compounds containing two groups of the formula X-ii-Clwherein one X is sulphur and the other is oxygen or wherein both Xs aresulphur. Moreover, although the bichloroformates are preferred becausethey are reactive and relatively inexpensive, it is not essential thatthey contain chlorine and one may use the corresponding bisbromoformatesor bisiodoformates.

As the diisocyanate one may employ any of the aliphatic, aromatic, orheterocyclic compounds containing two isocyanate (NCO) groups preferablyseparated by at least two carbon atoms. The diisocyanates may besubstituted if desired with non-interfering (non-function) substituentssuch as ether groups, thioether groups, sulphone groups, etc. Typicalexamples of compounds in this category are listed below merely by way ofillustration and not limitation: lEthylene diisocyanate, propylenediisocyanate, butylene diisocyanate, trimethylene diisocyanate,tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylenediisocyanate, decamethylene diisocyanate, cyclohexylene diisocyanate,bis(Z-isocyanatoethyl) ether, bis(2-isocyanatoethyl) ether of ethyleneglycol, o-phenylene diisocyanate, m-phenylene diisocyanate, p-phenylenediisocyanate, tolylene-2,4-diisocyanate, tolylene-Z,6-diisocyanate,3,3'-bitolylene-4,4-diisocyanate, i.e.,

CH3 CH3 diphenyl ether-4,4'-diisocyanate, i.e.,

3,5,3',5'-bixylylene-4,4-diisocyanate, i.e.,

R R l (R is CHa) diphenylmethane-4,4'-diisocyanate, i.e.,

biphenylene diisocyanate, 3,3-dimethoxy-biphenylene- 4,4-diisocyanate,naphthalene diisocyanates, polymethyl polyphenyl isocyanates, etc. It isalso evident that the sulphur analogues of these compounds may be usedand such are included within the spirit of the invention. Thus forexample, instead of using the compounds containing two NCO groups onemay use their analogues containing either two NCS groups or one NCOgroup and one NCS group. Another point to be made is that it is withinthe spirit of the invention to utilize the derivatives which yield thesame products with compounds containing active hydrogen as do theisocyanates. Particular reference is made to the biscarbamyl chlorideswhich may be used in place of the diisocyanates. Thus one may use any ofthe above-designated compounds which contain carbamyl chloride groups(N( i-c1) or their sulphur analogues in place of the isocyanate groups.

Among the preferred compounds are the aliphatic diisocyanates, forexample, those of the type wherein n has a value from 2 to 12. Otherpreferred compounds are the toluene diisocyanates, xylylenediisocyanates, and diphenylmethane-4,4'-diisocyanate which may also betermed methylene-bis(p-phenylisocyanate).

There has been set forth above a comprehensive disclosure of thepreferred types of complementary agents, that is, diamines, diols,diacid chlorides, bischloroformates, diisocyanates, and theirequivalents. Although it is preferred to use these agents for optimumresults, they are by no means the only compounds which may be used. Theinvention in its broadest aspect includes the application of many othertypes of complementary agents which have the ability to formcondensation polymers when applied by the disclosed procedures. Variousexamples are thus set forth of other types of compounds which may beused.

Polysulphonamides-forrned by conjoint use of a diamine and a disulphonylchloride. A typical example in this category involves applying to thewool an aqueous solution of a diamine, followed by applying to the woola disulphonyl chloride dissolved in benzene, toluene, or other inert,essentially water-immiscible solvent. Any of the diamines abovedescribed may be used in conjunction with such disulphonyl chlorides asbenzene-1,3-disulphonyl chloride, biphenyl-4,4-disulphonyl chloride,toluene disulphonyl chlorides or aliphatic compounds such as those ofthe formula wherein n has a value from 2 to 12. Related polymers can beformed by applying these disulphonyl chlorides (as Component B) inconjunction with such compounds as urea, guanidine, thiourea, biuret,dithiobiuret, or the like as Component A.

Polysulphonatesformed by the conjoint use of a diol and a disulphonylchloride. In a typical example in this area, an aqueous solution of adiolpreferably in the form of its alkali-metal salt-is first applied tothe wool, followed by application of a disulphonyl chloride in inert,essentially water-immiscible solvent. For this purpose one may use anyof the diols and disulphonyl chlorides ex emplified above. A variant ofthis procedure is to use the corresponding dithiol in place of the diol,thus to form a polythiolsulphonate.

An alternative to the diacid chlorides is the use of mixed anhydrides ofthe corresponding dicarboxylic acids with monobasic acids such astrifluoroacetic acid, dibutylphosphoric acid, or the like. Such mixedanhydrides may be employed, for example, as Component B in conjunctionwith a diamine, diol, or dithiol as Component A to form polyamides,polyesters, or polythiolesters, respectively.

Another plan involves the use of urea, thiourea, biuret, dithiobiuret,guanidine, or the like (as Component A) in conjunction with diacidchlorides as Component B to form polyureas, polythioureas, etc.

The invention is further demonstrated by the following illustrativeexamples.

The tests for shrinkage referred to in the examples were conducted inthe following Way: The W001 samples were milled at 1700 rpm. for 2minutes at 4042 C. in an Accelerotor with 0.5% sodium oleate in aqueoussolution, using a liquor-to-wool ratio of to 1. After this washingoperation the samples were measured to determine their area and theshrinkage was calculated from the original area. With this severeWashing method, samples of control (untreated) wool cloth gave an areashrinkage of 48%. The Accelerotor is described in the American DyestulfReporter, vol. 45, p. 685, Sept. 10, 1956.

The tests for water repellency referred to in the examples wereconducted as follows: The cloth sample was laid fiat and drops of waterplaced on it and the cloth then covered with an upturned beaker. Thesystem was observed at intervals to note the time required for the dropsto penetrate into the cloth. With an untreated cloth sample, water dropspenetrated in to minutes.

Tests for oil repellency were performed as above described except usingdrops of mineral oil instead of water. With the untreated cloth themineral oil drops penetrated instantly.

Example l.-Application of water-repellent (A) SOLUTIONS Solution I: 4%hexamethylene diamine in water. Solution II: 2% sebacoyl chloride and 2%behenoyl chloride in carbon tetrachloride.

(B) APPLICATION OF SOLUTIONS A sample of wool cloth was immersed insolution I for 30 seconds, run through squeeze rolls to remove excessliquid, immersed for 30 seconds in solution II, run through squeezerolls to remove excess liquid, given a 15-minute wash in warm water anddetergent, rinsed in water, and dried in air.

(C) RESULTS The treated wool displayed a weight increase of 7.2% and onwashing in the Accelerotor exhibited an area shrinkage of 13.6%.

In the water-repellency test it was found that water drops did notpenetrate the treated fabric for 8 hours or longer.

Example 2.Application of water-repellent Solution I: 4% hexamethylenediamine in water.

Solution H: 3% sebacoyl chloride and 3% polyethylene (molecular weightabout 5,000 to 10,000) in carbon tetrachloride.

Wool cloth was treated with solutions I and II as described in Example1, part B.

The treated cloth displayed a weight increase of 6.7% and on washing inthe Accelerotor exhibited an area shrinkage of 4%.

In the water-repellency test it was found that water drops did notpenetrate into the treated fabric for 8 hours or longer.

Example 3.Application of water-repellent Solution 1: 3% polyethyleneemulsion and 4% hexamethylene diamine in water. (The 3% polyethyleneemulsion contained polyethylene of molecular weight about 5,000 to10,000, 5% of alkyl aryl polyethylene glycol, 1.5% potassium hydroxidesolution, and 73.5 water.)

Solution I: 3% sebacoyl chloride in carbon tetrachloride.

Wool cloth was treated with solutions I and II as described in Example1, part B.

The treated cloth displayed a weight increase of 3.9% and on washing inthe Accelerotor exhibited an area shrinkage of 12.6%.

In the water-repellency test, water drops did not penetrate into thetreated cloth for 8 hours or longer.

Example 4.-Application of a soil-repellent Three runs were carried out,using the following solutions:

RUN A Solution I: 2% hexamethylene diamine in water plus 4% 'Na CO and 4ml. (per 100 ml. of solution) of a soil-repellent.

Solution 11: 3% sebacoyl chloride in carbon tetrachloride.

RUN B Solution I: 2% hexamethylene diamine in water plus 4% Na CO and 8ml. (per 100 ml. of solution) of a soilrepellent.

Solution II: 3% sebacoyl chloride in carbon tetrachloride.

RUN C Solution 1: 3% sebacoyl chloride in carbon tetrachloride.

Solution II: 2% hexamethylene diamine plus 4% Na CO and 8 ml. (per ml.of solution) of a soilrepellent.

The soil repellent used in these runs was a product designated as PC-139available from Minnesota Mining and Manufacturing Company and believedto be an emulsion containing as the active ingredient a polymerizedperfluoro acrylate ester.

Wool cloth was treated with the solutions as described in Example 1,part B. Weight increases and shrinkages (after Accelerotor washing) ofthe products were as follows:

Weight Increase, Percent Area Shrinkage, Percent ceno The treatedfabrics displayed excellent oiland waterrepellency. In theoil-repellency test, oil drops did not penetrate into the fabric for 7days; in the water-repellency test, water drops did not penetrate intothe fabric for over 12 hours. It was also found that the samples whichhad been washed in the Accelerotor (this represents a very severewashing) retained their oiland water-repellency essentially unimpaired.

Example 5.Application of water-repellent Solution I: 4% hexamethylenediamine in water. Solution II: 3% sebacoyl chloride and 4% of apolymerized methyl hydrogen siloxane of the formula:

H is-as Wool cloth was treated with solutions I and II as described inExample 1, part B. The treated cloth displayed a weight increase of 2.7%and on washing in the Accelerotor exhibited an area shrinkage of 12.6

In the water-repellency test it was found that it required 12 hours forwater drops to penetrate into the treated fabric.

Example 6.-Application of water-repellent Solution 1: 4% hexamethylenediamine in water. Solution II: 3% sebacoyl chloride plus 4% ofpolydimethyl siloxane.

Wool cloth was treated with solutions I and H as described in Example 1,part B. The treated cloth displayed a weight increase of 2.9% and onwashing in the Accelerotor exhibited an area shrinkage of 13.5%.

In the water-repellency test it was found that it required 12 hours forthe water drops to penetrate into the treated fabric.

Example 7.Application of water-repellent Solution I: 4% hexamethylenediamine in water. Solution II: 3% sebacoyl chloride and 4% carnauba waxin carbon tetrachloride.

15 16 Solution II: 3% sebacoyl chloride and 0.05% Heliogen A sample ofthe product which had been subjected blue (a phthalocyanine pigment-Cl.pigment blu 15, only to the process wash (following application of solu-74160) in a Volatile Petroleum hydrocarbon tions I and II) and a sampleof the product which had distillate, 133 to been washed in theAccelerotor were subjected to tests (B) APPLICATION OF SOLUTIONS 5 forresistance to attack by moths. As a control, a sample of the untreatedfabric was also subjected to the tests.

A sample of wool cloth was Immersed m Sohmon I In the tests, fabricsamples of identical size were placed for 15 seconds, run throughsqueeze rolls to remove excess liquid, immersed for 15 seconds insolution II, and m a vessel together Wlth f P bcetle larvae, 51X runthrough squeeze rolls to remove excess liquid. The Week 14 days,examlnatfqfl Was made 0 treated cloth was then given a 15-minute processwash in 10 termlne moftallty 0f the beetles, Vlslble f g the warm waterand detergent, rinsed in water, and dried in fabric, and the excrement0f the es Welghed. The air. results are tabulated below:

Visible Weight of Sample Mortality damage excrement to fabric Treatedfabric All dead None 1 mg. Treated fabric, washed in Accelerotor 4 dead,6 in abnormal condition do 1 mg. Untreated fabric All alive and normalYes 10 mg.

RESULTS Example 11.-Application of Insecticide and Soil- The treatedcloth displayed a weight increase of 2% and Repellent on washin; in theAccelerotor exhibited an area shrink- Solution I: 3% hexamethylemdiamine 6% z 3 and ageo 18 0. is I The treated fabric displayed auniform pastel blue color fgjf 3 3 Polymenzed perfluoro butyl acry whichremamed fast dmng the Pmess Wash (Mbwmg Solution n: 3% sebacoyl chlorideand 1% of a dieldrin application of solutions I and II) and during thesucceeding wash in the Accelerotor. It is to be noted that concentrate(20%) m toluene the Heliogen blue used in this experiment is not Woolcloth was treated with solutions I and II as destannve for W001 scribedin Example 1, part B. The treated cloth displayed Example 9.Applicationof soil-repellent a weight increase of 2% and on washing in theAccelerotor exhibited an area shrinkage of 13.5%.

The treated fabric displayed excellent oil and water repellency. In theoil-repellency test, oil drops did not penetrate into the fabric for 60hours; in the water-re- Solution I: 3% hexamethylene diamine, 6% Na COand 1% of a soil-repellent in water. Solution II: 3% sebacoyl chloridein carbon tetrachloride.

The soil-repellent used in this test was a commercial pellency test,water drops did not penetrate into the fabric product PC-208 availablefrom the Minnesota Mining for 6 hours. It was also found that when thesamples and Manufacturing Company and believed to be a polymhad beenwashed in the Accelerotor (which represents a erized perfluoro butylacrylate. very severe washing), their oil and water repellency re- Woolcloth was treated with solutions I and II as demained essentiallyunimpaired. scribed in Example 8, part B. The treated cloth displayedSamples of the product which had been subjected only a weight increaseof 216% and on washing in the Acceleroto the process wash (followingapplication of solutions tor exhibited an area shrinkage of 12.6%. I andII) and a sample of the product which had been In the repellency testsit was found that oil drops and washed in the Accelerotor were subjectedto tests for water drops required and over 12 hours, respectively,resistance to attack by moths, as described in Example to penetrate intothe fabric. 10. The results are tabulated below:

Visible Weight of Sample Mortality damage excrement to fabric Treatedfabric All dead N0ne 1 mg. Treated fabric washed in Accelerotor 6 dead,4 abnormal ..do 1 mg. Untreated fabric All alive and normaL Yes 10 mg.

Example 10.Application of insecticide Example l2.,--Application ofinsecticide Solution 1: 3% hexamethylene diamine and 6% Na CO Solution1: 3% hexamethylene diamine, 6% Na CO and in water. 1% of awater-soluble insecticide (pentachlorodihy- Solution II: 3% sebacoylchloride and 1% of a 20% 60 droxy-triphenylmethane sodium sulphonate) inwater.

solution of dieldrin, in toluene. Solution II: 3% sebacoyl chloride intoluene.

Dieldrin is the common name of the compound:1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8 Wool cloth wastreated with solutions I and II asdeoctahydro-l,4,5,S-dimethano-naphthalene. scribed in Example 1, part B.The treated cloth displayed a weight increase of 2% and on washingexhibited an Wool cloth was treated with solutions I and II as deareashrinkage of 23.5%. scribed in Example 8, part B. The treated clothdisplayed The products were tested for resistance to attack by a weightincrease of 2.0% and on washing in the Acmoths as described in Example10. The results are tabcelerotor exhibited an area shrinkage of 4.9%.ulated below:

Visible Weight 01 Sample Mortality damage excrement to fabric Treatedfabric 5 dead, 5 abnormal None 1 mg.

Treated fabric washed in Accelerotor 2 dead, some larvae normal Slight 3mg.

Example 13.-Application of soil-repellent RUN A Solution I: 2%hexamethylene diamine and 4% Na CO in water.

Solution H: 3% sebacoyl chloride plus 1% of EC-13 9 (described inExample 4) in a volatile petroleum hydrocarbon distillate.

RUN B Solution I: 2% hexamethylene diamine and 4% Na CO in water.

Solution II: 3% sebacoyl chloride plus 5% of FC13 9 (described inExample 4) in a volatile petroleum hydrocarbon distillate.

Samples of wool cloth were treated with the solutions as described inExample 8, part B.

It was found that the products had excellent oiland water-repellency asoil drops and water drops did not penetrate the treated fabrics for 24hours.

Example 14.Application of water-repellent Solution 1: 2.5% hexamethylenediamine and 5% sodium carbonate in water.

Solution II: 3% sebacoyl chloride and 2% para- (trifluoromethyl) benzoylchloride in xylene.

Samples of wool cloth 'were treated with the solutions as described inExample 1, part B.

It was found that the products had excellent waterrepellency as waterdrops remained on the fabric surface more than 12 hours without wettingthe fabric.

The present invention finds its greatest field of utility in thetreatment of wool textiles, particularly because it yields a dualbenefit, that is, the wool is provided with a fixed deposit of finishingagent and the wool is also shrinkproof. However, in its broad aspect theinvention encompasses the treatment of any other type of fibrousmaterial,

typical examples being animal hides; leather; animal hair; cotton; hemp;jute; ramie; flax; wood; paper; synthetic cellulosic fibers such asviscose, cellulose, acetate, and cellulose acetate-butyrate; caseinfibers; polyvinyl alcoholprotein fibers, alginic fibers; glass fibers;asbestos; and organic non-cellulosic fibers such as poly(ethylene glycolterephthalate), polyacrylonitrile, polyethylene, polyvinyl chloride,polyvinylidene chloride, etc. With all such fibrous materials theinvention is of usefulness to provide them with fixed deposits offinishing agents whether or not shrinkage protection is also afforded.

Having thus described the invention, what is claimed is:

1. A process for treating a fibrous material which comprises seriallyapplying to said material a pair of complementary direct-acting,organic, polyurea-forming intermediates in separate phases of limitedmutual solubility,

at least one of said phases also containing a textile finishing agent.

2. A process for shrinkproofing wool without significant impairment ofits hand and for concomitantly applying thereto a textile finishingagent, which comprises serially impregnating wool with two solutions,

one solution containing a diamine dispersed in water,

the other solution containing a diisocyanate dispersed in an inert,volatile, essentially water-immiscible solvent,

at least one of said solutions also containing a textile finishingagent,

the said diamine and diisocyanate reacting to form in situ on the woolfibers a resinous polyurea having enmeshed therein the said finishingagent.

3. The process of claim 2 wherein the finishing agent is an insecticide.

4. The process of claim 2 wherein the finishing agent is asoil-repellent.

5. The process of claim 2 wherein the finishing agent is awater-repellent.

6. The process of claim 2 wherein the finishing agent is a coloringmaterial.

7. The process of claim 2 wherein the finishing agent comprises aninsecticide and a soil-repellent.

8. A modified wool fiber which exhibits improved shrinkage properties ascompared with the unmodified wool fiber and which is provided with adurable finish, comprising wool fiber having a polyurea formed in situthereon and chemically bonded to the wool,

said polyurea having a textile finishing agent enmeshed therein andthereby fixed to said wool fiber.

9. The product of claim 8 wherein the finishing agent is an insecticide.

10. The product of claim 8 \wherein the finish'mg agent is asoil-repellent.

11. The product of claim 8 wherein the finishing agent is awater-repellent.

12. The product of claim 8 wherein the finishing agent is a coloringmaterial.

13. The product of claim 8 wherein the finishing agent comprises aninsecticide and a soil-repellent.

14. A process for shrinkproofing wool without significant impairment ofits hand and for concomitantly applying thereto a textile finishingagent, which comprises serially impregnating wool with two solutions,

one solution containing a diamine dispersed in water,

the other solution containing a diacid chloride dispersed in an inert,volatile, essentially water-immiscible solvent,

at least one of said solutions also containing a textile finishingagent,

the said diamine and diacid chloride reacting to form in situ on theW001 fibers a resinous polyamide having enmeshed therein the saidfinishing agent.

15. The process of claim 14. wherein the finishing agent is aninsecticide.

16. The process of claim 14 wherein the finishing agent is asoil-repellent.

17. The process of claim 14 wherein the finishing agent is awater-repellent.

18. The process of claim 14 wherein the finishing agent is a coloringmaterial.

19. The process of claim 14 wherein the finishing agent comprises aninsecticide and a soil-repellent.

References Cited UNITED STATES PATENTS 3,078,138 2/1963 Miller et a1.8-l28 FOREIGN PATENTS 579,340 7/ 1946 Great Britain.

NORMAN G. TORCHIN, Primary Examiner. I. CANNON, Assistant Examiner.

US. Cl. X.R. 894.1, 115.5, 116.2, 120, 127.6, 128, 129

1. A PROCESS FOR TREATING A FIBROUS MATERIAL WHICH COMPRISES SERIALLYAPPLYING TO SAID MATERIAL A PAIR OF COMPLEMENTARY DIRECT-ACTING,ORGANIC, POLYUREA-FORMING INTERMEDIATES IN SEPARATE PHASES OF LIMITEDMUTUAL SOLUBILITY, AT LEAST ONE OF SAID PHASES ALSO CONTAINING A TEXTILEFINISHING AGENT.